CN118852584B - A composite anhydride modified UV-curable epoxy acrylate and its preparation method and application - Google Patents
A composite anhydride modified UV-curable epoxy acrylate and its preparation method and applicationInfo
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- CN118852584B CN118852584B CN202410979280.9A CN202410979280A CN118852584B CN 118852584 B CN118852584 B CN 118852584B CN 202410979280 A CN202410979280 A CN 202410979280A CN 118852584 B CN118852584 B CN 118852584B
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Abstract
本发明公开了一种复合酸酐改性可UV光固化环氧丙烯酸酯及其制备方法和应用；所述制备方法为包括以下步骤：将戊二酸酐、马来酸酐、邻苯二甲酸酐、丙烯酸、丙烯酸羟乙酯、环氧树脂、部分催化剂、部分阻聚剂搅拌加热到75℃～80℃并保温0.8～1.2h，然后分段升温、分批加入剩余催化剂和剩余阻聚剂，最终升至115～125℃反应4～5h，得到复合酸酐改性可UV光固化环氧丙烯酸酯。制备方法，价格低廉，产品成本低，反应过程不使用任何溶剂，降低VOC排放；制备得到的环氧丙烯酸酯成膜后具有较高的官能度、较好的硬度、附着力、柔韧性、抗冲击性和耐化学品性。
The present invention discloses a composite anhydride-modified UV-curable epoxy acrylate, its preparation method, and application. The preparation method comprises the following steps: stirring and heating glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, a portion of a catalyst, and a portion of a polymerization inhibitor to 75°C to 80°C and maintaining the temperature for 0.8 to 1.2 hours; then gradually increasing the temperature, adding the remaining catalyst and polymerization inhibitor in batches, and finally raising the temperature to 115 to 125°C and reacting for 4 to 5 hours to obtain the composite anhydride-modified UV-curable epoxy acrylate. The preparation method is inexpensive and has low product cost. The reaction process does not use any solvent, thereby reducing VOC emissions. The epoxy acrylate prepared exhibits high functionality, good hardness, adhesion, flexibility, impact resistance, and chemical resistance after film formation.
Description
Technical Field
The invention relates to the field of preparation of ultraviolet light curing epoxy acrylate coating, in particular to a composite anhydride modified ultraviolet light curing epoxy acrylate, a preparation method and application thereof.
Background
The Ultraviolet (UV) curing technology refers to a process that under the irradiation of ultraviolet light, a photoinitiator in a system absorbs energy and then generates free radicals or cations, so that an oligomer containing active groups and an active diluent are initiated to undergo chemical reactions such as grafting, polymerization, crosslinking and the like, and further the surface of a substrate is promoted to be rapidly cured into a film. Different from the traditional coatings such as solvent type, water-based, thermosetting and the like, the UV curing technology has the advantages that the curing speed of a paint film is high, the solvent is not needed, the operation is simple, and the curing process is not easily influenced by factors such as temperature, environment and the like. Along with the gradual transition of the industry of China to the green, environment-friendly, efficient and energy-saving and intelligent directions, the industrialized application of the ultraviolet curing technology is rapidly developed.
Epoxy acrylate resin is the most commonly used UV light-cured resin, bisphenol A epoxy acrylate is the type with the fastest curing speed in epoxy acrylate oligomer, and is the most applied type, and due to the existence of a rigid benzene ring structure in the structure, the UV curing coating film has large brittleness and poor flexibility, and has poor weather resistance, light aging resistance and yellowing resistance. In order to solve the defects, chinese patent No. 102295730A discloses a synthesis method of intramolecular toughening epoxy vinyl ester resin, which comprises the steps of firstly reacting long-chain saturated dibasic acid with flexible dihydric alcohol to prepare carboxyl-terminated long-chain saturated dibasic acid monoester, and then reacting the monoester with epoxy resin and unsaturated monocarboxylic acid until the acid value is reduced to below 10 mgKOH/g. The method has the advantages that the flexible molecular chain is introduced into the main chain of the resin, so that the toughness of the resin is improved, and the method has the defects that the introduction of the dibasic acid monoester can increase the molecular weight and the viscosity of the resin, the dosage is large, the viscosity of the resin is increased, the storage is unstable, the hardness of a coating film is reduced, and the toughening effect is poor. The patent application with publication number CN104558522A discloses a modification method of modified epoxy acrylate, which adopts bisphenol A type epoxy resin and 1, 2-cyclohexanediol diglycidyl ether to react to generate modified epoxy resin, the synthesis method is that the two materials and a catalyst are added into a reaction vessel, stirred and heated to 80-90 ℃, acrylic acid and polymerization inhibitor mixture are gradually added dropwise within 0.5-1h, and then the temperature is gradually increased until the acid value is reduced to below 3.0mgKOH/g, thus obtaining the modified epoxy acrylate. Although the patent solves the problems of high resin viscosity, high film brittleness and poor flexibility, the patent achieves the aim by mixing 1, 2-cyclohexanediol diglycidyl ether diacrylate into common epoxy acrylic resin in a physical blending mode, and the hardness of the film is easy to reduce. Therefore, development of a modified epoxy acrylic resin with high hardness, high toughness and good flexibility is a technical problem which is urgently needed to be solved in the field.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of the composite anhydride modified UV light-curable epoxy acrylate, which has the advantages of low price, low product cost, no solvent in the reaction process, reduction of VOC emission, and higher hardness, excellent adhesive force, flexibility, impact resistance and chemical resistance after the prepared epoxy acrylate is cured into a film.
It is another object of the present invention to provide a composite anhydride modified UV light curable epoxy acrylate.
Still another object of the present invention is to provide an application of the above composite acid anhydride modified UV photo-curable epoxy acrylate for preparing a coating, and a cured coating film has characteristics of high hardness, excellent flexibility and impact resistance, chemical resistance, heat resistance and fast curing speed.
The aim of the invention is achieved by the following technical scheme:
The invention provides a preparation method of composite anhydride modified UV light-curable epoxy acrylate, which comprises the following steps:
(1) The raw materials are weighed according to the following formula in parts by weight:
(2) Stirring and heating glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, partial catalyst and partial polymerization inhibitor to 75-80 ℃ and preserving heat for 0.8-1.2 h, then heating in sections, adding the rest catalyst and the rest polymerization inhibitor in batches, and finally raising the temperature to 115-125 ℃ to react for 4-5 h to obtain the composite anhydride modified UV photo-curable epoxy acrylate;
The weight of the partial catalyst is 55-65% of the total weight of the catalyst, and the weight of the partial polymerization inhibitor is 55-65% of the total weight of the polymerization inhibitor.
Preferably, the epoxy resin is one of epoxy resins E51, E44, F51, 170, 128, R-828, S-21 and BD-20.
Preferably, the catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N dimethylbenzylamine and triphenylphosphine.
Preferably, the polymerization inhibitor is at least one of p-hydroxyanisole, p-benzoquinone, methyl hydroquinone, hydroquinone and 2, 5-dimethyl hydroquinone.
Preferably, the step-wise heating and the batch addition of the residual catalyst and the residual polymerization inhibitor are specifically as follows:
heating to 8-10 ℃ every 0.8-1.2 h, and adding the residual catalyst and the residual polymerization inhibitor for 4-5 times.
The invention also provides a composite anhydride modified UV light-curable epoxy acrylate, which comprises the following components in parts by weight:
The invention also provides application of the composite anhydride modified UV light-curable epoxy acrylate, which is used for preparing a coating.
Preferably, the coating comprises 65-87 parts of composite anhydride modified UV curable epoxy acrylate, 10-30 parts of reactive diluent and 3-5 parts of photoinitiator.
Preferably, the reactive diluent is one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate and triethylene glycol diacrylate.
Preferably, the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide and 1-hydroxycyclohexyl phenyl ketone.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the invention, glutaric anhydride, maleic anhydride and phthalic anhydride are compounded, and react with hydroxyethyl acrylate to generate a carboxyl intermediate containing vinyl, a monocarboxylic acid intermediate containing vinyl is introduced, and a rigid benzene ring is introduced, so that the vinyl functionality and the rigid benzene ring content of the modified epoxy acrylic resin product are improved, the crosslinking density of a UV cured coating film is improved, and the hardness and the chemical resistance are improved.
(2) According to the invention, glutaric anhydride, maleic anhydride and phthalic anhydride are compounded, the proportion is reasonably limited, the rigid structure and the flexible long chain are combined, and the problems of high hardness, high flexibility and high impact resistance of the UV cured coating are optimized and improved.
(3) The UV light-curable epoxy acrylate prepared by the one-step method has the advantages of simple synthesis process, mild reaction conditions, low industrial operation difficulty, wide raw material sources, low cost and low preparation cost of resin, and the coating prepared by the resin can be directly applied to UV curing and has a prospect of large-scale industrial production.
(4) The composite anhydride modified UV light-curable epoxy acrylate can be applied to various fields such as primer finishing paint, plastic paint, printing ink and the like, and the coating has high crosslinking density, high hardness, good flexibility and excellent chemical resistance.
Drawings
FIG. 1 is an infrared spectrum of a composite anhydride-modified UV curable epoxy acrylate in example 1 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of a composite anhydride-modified UV curable epoxy acrylate in example 1 of the present invention.
FIG. 3 is a gel chromatogram of a composite anhydride-modified UV curable epoxy acrylate in example 1 of the present invention.
FIG. 4 is a schematic diagram of the synthetic scheme of the composite anhydride-modified UV curable epoxy acrylate of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
The comparative examples in each example were prepared by substituting the modified epoxy acrylate of the present invention with EA resin from North Xinjia Baoli chemical group Co., ltd. As the oligomer component of the ultraviolet light curable coating, and the other components and proportions were the same as those in the examples.
In the following examples, the properties of UV-curable resins and photo-curable coatings were measured by measuring the viscosity of the resins using a rotational viscometer of the type NDJ-8 according to GB/T21059-2007, the acid value of the resins according to GB/T6753-2008, the hardness of the coating films according to GB/T6739-2006, the adhesion of the coating films according to GB-T9286-1998, the water resistance of the coating films according to GB/T5209-1985 by a room temperature immersion method, the alcohol resistance of the coating films according to GB/T1763-79, the acid/alkali resistance of the coating films according to GB/T9274-2009, the impact resistance of the coating films according to GB/T20624.2-2006, and the flexibility of the coating films according to GB/T1731-1993 by a QTY-10A paint film bending tester.
Example 1
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are yellowish transparent and clear appearance, an acid value of 2.7mgKOH/g and a viscosity of 124500 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating is as follows in parts by mass:
Adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine having a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were tested as shown in Table 3, as compared with the properties of the paint 1 of the simultaneous example and the EA resin of the same market.
(4) Table 3:
As can be seen from Table 3, compared with the existing product, the composite anhydride modified UV curable epoxy acrylate resin provided by the invention has the advantages that the resin viscosity is reduced, the hardness of the obtained cured film is moderate, the adhesive force of a paint film is improved, the flexibility and the impact resistance are greatly improved, and meanwhile, the composite anhydride modified UV curable epoxy acrylate resin has excellent chemical resistance.
FIG. 1 is an infrared spectrum of the composite anhydride-modified UV-curable epoxy acrylate of example 1, showing that the peak of the epoxy group at 910cm -1 disappeared, the peak of the ester bond at 1719cm -1 appeared, the peak assigned to the hydroxyl group at 3467cm -1 was enhanced, and the characteristic peak of the carbon-carbon double bond at 1607cm -1 appeared, which demonstrates the ring opening of the epoxy resin and the successful grafting of the carboxyl intermediate with acrylic acid, and the characteristic peak of the anhydride carbonyl group at 1760cm -1、1850cm-1 was not seen in the figure, indicating that the anhydride group was also reacted in the process.
FIG. 2 is a nuclear magnetic resonance spectrum of a compound anhydride-modified UV-curable epoxy acrylate of example 1, wherein 7.7-7.8ppm of benzene ring proton peaks on phthalic anhydride, 7.1ppm and 6.8ppm of benzene ring proton peaks on epoxy resin, 5.9-6.3ppm of double bond proton peaks on hydroxyethyl acrylate, hydroxyl groups generated by esterification reaction of anhydride and hydroxyethyl acrylate are located at 5.4ppm,4.8ppm of double bond proton peaks of maleic anhydride, and methylene peaks on glutaric anhydride and hydroxyethyl acrylate are located at 3.7-4.5ppm, which proves that anhydride and hydroxyethyl acrylate are successfully grafted on E51.
FIG. 3 is a gel chromatogram of the composite anhydride-modified UV-curable epoxy acrylate of example 1, from which data for the obtained UV-curable epoxy acrylate synthesized in this example 1 were obtained, having a number average molecular weight (Mn) of 1282g/mol and a weight average molecular weight (Mw) of 1321g/mol.
FIG. 4 is a reaction scheme and a molecular structural diagram in example 1, wherein a compound anhydride reacts with hydroxyethyl acrylate to generate a carboxyl-containing intermediate, and then the carboxyl-containing intermediate reacts with acrylic acid and epoxy resin E51 in a ring-opening manner, so that the variety of anhydride is more, and the possibility of the molecular structure generated in the reaction process is more.
Compared with the resin prepared in the patent 1 (CN 102295730A), the resin prepared in the invention has the advantages of low viscosity, compatible film hardness and flexibility, low reaction process temperature, simple process and good resin storage stability. Compared with the comparative patent 2 (CN 104558522A), the resin prepared by the invention has uniform components, can coordinate the contradiction between high coating hardness and high toughness, and has low resin production cost and simple process.
Example 2
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are yellowish transparent and clear appearance, an acid value of 1.8mgKOH/g and a viscosity of 118350 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating is as follows in parts by mass:
Adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine having a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were tested as shown in Table 6, as compared with the properties of the paint 2 of the simultaneous example and the EA resin of the same market.
(4) Table 6:
Example 3
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are yellowish transparent and clear appearance, an acid value of 1.5mgKOH/g and a viscosity of 115600 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating is as follows in parts by mass:
adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine having a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were tested as shown in Table 9, as compared with the properties of the paint 3 of the same example and the EA resin of the same market.
(4) Table 9:
example 4
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are yellowish transparent and clear appearance, an acid value of 2.5mgKOH/g and a viscosity of 143150 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating is as follows in parts by mass:
Adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine at a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were tested as shown in Table 12, as compared with the properties of the paint 4 of the simultaneous example and the EA resin of the same market.
(4) Table 12:
example 5
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are yellowish transparent and clear appearance, an acid value of 2.7mgKOH/g and a viscosity of 138550 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating material in parts by mass is shown in table 14 below:
adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine having a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were tested as shown in Table 15, as compared with the properties of the paint 5 of the simultaneous example and the EA resin of the same market.
(4) Table 15:
example 6
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are yellowish transparent and clear appearance, an acid value of 1.9mgKOH/g and a viscosity of 134800 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating material in parts by mass is shown in table 17 below:
Adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine having a power of 600mW/cm 2 and a wavelength of 365nm, and the properties of the coated film were measured as shown in Table 18, and compared with those of the paint 6 of the same example and the same EA resin as in the market.
(4) Table 18:
Example 7
(1) The preparation of the composite anhydride modified UV curable epoxy acrylate comprises the following steps of preparing the composite anhydride modified UV curable epoxy acrylate resin, wherein the raw material formula comprises the following components in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are that the appearance is white, transparent and clear, the acid value is 2.1mgKOH/g, and the viscosity is 103850 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating material in parts by mass is shown in table 20 below:
Adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine at a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were tested as shown in Table 21, as compared with the properties of the paint 7 of the simultaneous example and the EA resin of the same market.
(4) Table 21:
Example 8
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are that the appearance is white, transparent and clear, the acid value is 1.6mgKOH/g, and the viscosity is 101450 mPa.s.
(3) Preparation of UV curable coating:
the configuration composition of the UV-curable coating material in parts by mass is as follows in table 23:
Adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine at a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were tested as shown in Table 24, as compared with the properties of the paint 8 of the simultaneous example and the EA resin of the same market.
(4) Table 24:
Example 9
(1) Preparation of the composite anhydride-modified UV-curable epoxy acrylate resin of this example comprises the following raw materials in percentage by mass:
the preparation process of the composite anhydride modified UV curable epoxy acrylate comprises the following steps:
the glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin E51, tetraethylammonium bromide (accounting for 60wt% of the total catalyst) and para-hydroxyanisole (accounting for 60wt% of the total polymerization inhibitor) with the compositions are added into a four-neck flask with a stirring paddle, a thermometer and a condenser tube, heated to 75 ℃ and kept for 1h, 10wt% of the tetraethylammonium bromide and the para-hydroxyanisole are added every 1h, and then gradually heated to 83 ℃,90 ℃,97 ℃ and 105 ℃ and finally heated to 120 ℃ and then kept for 4-5h, the acid value is measured to be reduced to below the theoretical value, and the composite anhydride modified UV curable epoxy acrylate is obtained after cooling and discharging.
(2) The physical and chemical properties of the composite anhydride modified UV curable epoxy resin are that the appearance is white, transparent and clear, the acid value is 2.0mgKOH/g, and the viscosity is 97650 mPa.s.
(3) Preparation of UV curable coating:
The configuration composition of the UV-curable coating material in parts by mass is shown in table 26 below:
Adding the above formula material into a container, and dispersing at low speed for 10-15min at 600 r/min. After the paint was left standing without bubbles, it was coated on a wooden board, a glass board and a tin plate, respectively, with a four-side wet film coater, at a thickness of 25.+ -.2. Mu.m, and cured with a UV curing machine having a power of 600mW/cm 2 and a wavelength of 365nm, and the coating properties were measured as shown in Table 27, and compared with the properties of the paint 9 of the same example and the EA resin of the same market.
(4) Table 27:
in the above embodiment, the epoxy resin may be one of the epoxy resins E51, E44, F51, 170, 128, R-828, S-21, BD-20.
In the above embodiment, the catalyst may be at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N dimethylbenzylamine, and triphenylphosphine.
In the above embodiment, the polymerization inhibitor is at least one of p-hydroxyanisole, p-benzoquinone, methylhydroquinone, hydroquinone, and 2, 5-dimethylhydroquinone.
In the above embodiment, the reactive diluent may be one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate, and triethylene glycol diacrylate.
In the above embodiments, the photoinitiator may be at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, and 1-hydroxycyclohexyl phenyl ketone.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.
Claims (10)
1. The preparation method of the composite anhydride modified UV light-curable epoxy acrylate is characterized by comprising the following steps of:
(1) The raw materials are weighed according to the following formula in parts by weight:
(2) Stirring and heating glutaric anhydride, maleic anhydride, phthalic anhydride, acrylic acid, hydroxyethyl acrylate, epoxy resin, partial catalyst and partial polymerization inhibitor to 75-80 ℃ and preserving heat for 0.8-1.2 h, then heating in sections, adding the rest catalyst and the rest polymerization inhibitor in batches, and finally raising the temperature to 115-125 ℃ to react for 4-5 h to obtain the composite anhydride modified UV photo-curable epoxy acrylate;
The weight of the partial catalyst is 55-65% of the total weight of the catalyst, and the weight of the partial polymerization inhibitor is 55-65% of the total weight of the polymerization inhibitor.
2. The method for preparing a composite anhydride modified UV light curable epoxy acrylate according to claim 1, wherein the epoxy resin is one of epoxy resins E51, E44, F51, 170, 128, R-828, S-21, BD-20.
3. The method for preparing the composite anhydride modified UV-curable epoxy acrylate according to claim 1, wherein the catalyst is at least one of tetraethylammonium bromide, tetrabutylammonium bromide, N-dimethylbenzylamine and triphenylphosphine.
4. The method for preparing the composite anhydride modified UV-curable epoxy acrylate according to claim 1, wherein the polymerization inhibitor is at least one of para-hydroxyanisole, para-benzoquinone, methylhydroquinone, hydroquinone and 2, 5-dimethylhydroquinone.
5. The method for preparing the composite anhydride modified UV light-curable epoxy acrylate according to claim 1, wherein the steps of heating in sections, adding the residual catalyst and the residual polymerization inhibitor in batches are as follows:
heating to 8-10 ℃ every 0.8-1.2 h, and adding the residual catalyst and the residual polymerization inhibitor for 4-5 times.
6. The composite anhydride modified UV light-curable epoxy acrylate is characterized by comprising the following components in parts by weight:
7. Use of a composite anhydride-modified UV light curable epoxy acrylate according to claim 6 for the preparation of a coating.
8. The use according to claim 7, wherein the coating comprises 65-87 parts by weight of the composite anhydride modified UV curable epoxy acrylate, 10-30 parts by weight of the reactive diluent and 3-5 parts by weight of the photoinitiator.
9. The use according to claim 8, wherein the reactive diluent is one of tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, hexanediol diacrylate, triethylene glycol diacrylate.
10. The use according to claim 8, wherein the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, diphenyl (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone.
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|---|---|---|---|---|
| CN103087294A (en) * | 2011-10-28 | 2013-05-08 | 安庆飞凯高分子材料有限公司 | Modified epoxy acrylic acid resin, preparation method and uses thereof |
| CN106188497A (en) * | 2016-08-11 | 2016-12-07 | 安庆飞凯高分子材料有限公司 | A kind of synthetic method of modified epoxy acrylate resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103087294A (en) * | 2011-10-28 | 2013-05-08 | 安庆飞凯高分子材料有限公司 | Modified epoxy acrylic acid resin, preparation method and uses thereof |
| CN106188497A (en) * | 2016-08-11 | 2016-12-07 | 安庆飞凯高分子材料有限公司 | A kind of synthetic method of modified epoxy acrylate resin |
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